CN103539828A - Method of extracting hyodeoxycholic acid from leftovers of pig bile without bilirubin - Google Patents
Method of extracting hyodeoxycholic acid from leftovers of pig bile without bilirubin Download PDFInfo
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- CN103539828A CN103539828A CN201310449477.3A CN201310449477A CN103539828A CN 103539828 A CN103539828 A CN 103539828A CN 201310449477 A CN201310449477 A CN 201310449477A CN 103539828 A CN103539828 A CN 103539828A
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- bile acid
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- sus domestica
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Abstract
The invention discloses a method of extracting hyodeoxycholic acid from leftovers of pig bile without bilirubin. The method comprises the following steps: esterification of pig total bile acid, alcohol extraction, recrystallization, hydrolysis reaction and the like. By taking pig bile as an extracting raw material, the raw material of the pig bile is wide and easily available, so that the preparation cost is lowered. In the extracting process, methanol is selected as a solvent and an esterification reagent, the hydrolyzing and refining conditions of the methyl hyodeoxycholate are determined, and sodium hydroxide is taken as a base catalyst. The rate of charge of the raw material and the base catalyst is 1:2.5. Through the technical flow, the total yield of the hyodeoxycholic acid is over 40%.
Description
Technical field
The invention belongs to biological medicine technology field, relate to the preparation method of Hyodeoxycholic Acid, be specifically related to a kind of method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage.
Background technology
Bile is the product that human body or vertebrates liver cell secrete continuously, it is a kind of coloured alkaline liquid of viscosity with bitter taste, beyond its composition dewaters, mainly contain bile acide, cholate and bile pigment, also have in addition a small amount of cholesterol, lipid acid, Yelkin TTS, ionogen and protein etc.More common animal bile is generally bird gall, Fel Sus domestica, oxgall, Fel Ursi and Fel Serpentis etc. now.Bile acide is the main component of bile, account for 50%～70% of bile total amount, the physiological action of bile is mainly brought into play by bile acide exactly, when as medicine, that bile acide can be used for is analgesic, antispastic antibechic, regulate blood pressure, cardiac stimulant cholagogic, antibacterial anti-inflammatory and regulate immunity etc., and activity is strong, side effect is again little, cheap, is therefore subject to vast medication person's welcome.
In various animal biles, Fel Sus domestica is the most common and output is maximum, from ancient times, start to be just widely used in clinical, as by Fel Sus domestica treatment acute icteric infectious hepatitis, Whooping cough, acute enteritis and stomach ulcer etc., all can receive good therapeutic action.Main containing bile acids, bile pigment, Saliva Orthana, lipid and inorganics etc. in Fel Sus domestica, bile acide mainly comprises Hyodeoxycholic Acid, Iocholic acid, Chenodiol, 3 Alpha-hydroxies-6-oxygen-5 α-ursodeoxycholic acid and cholelith acid etc.Wherein Hyodeoxycholic Acid accounts for 40%, and Chenodiol accounts for 25%.
Hyodeoxycholic Acid, has another name called Taurohyodeoxycolic Acid, chemistry 3 α by name, and 6 alpha-dihydroxy--5 β-ursodeoxycholic acids, molecular formula is C
24h
40o
4, molecular weight 392.578, is white or micro-yellow powder slightly, bitter is micro-stench, is slightly dissolved in methyl alcohol, ethanol, and slightly soluble in acetone, atomic molten in ether, chloroform, water-soluble hardly, fusing point is 200～201 ℃.
Hyodeoxycholic Acid can suppress formation and the dissolved fat of cholic acid, reduces blood cholesterol and triglyceride level, is applicable to I a or I b type hyperlipidemia, atherosclerosis; Bordetella pertussis, diphtheria corynebacterium, streptococcus aureus etc. are had to certain bacteriostatic action, can be used as antiphlogistic drug, treatment chronic bronchitis, child virus upper respiratory tract infection etc.; This product can stimulate choleresis, makes bile thinning and do not increase amount of solid, is applicable to biliary tract inflammation, cholecystitis, cholelithiasis and other nonobstructive cholestasis, also can accelerate cholecystic radiopoaque medium and discharge liver and contribute to and develop; Still can promote enteron aisle steatolysis and liposoluble vitamin to absorb, can be used for the maldigestion that hepatobiliary disease causes.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind ofly take Fel Sus domestica and is the method for the separated Hyodeoxycholic Acid of raw material, and the method extraction process is simple, without specific installation, raw material sources are extensively easy to get, pollution to environment in leaching process is little, and the product purity making is high, and product recovery rate is high.
For solving the problems of the technologies described above, the technical scheme that Bian of the present invention gets is as follows:
A method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage, comprises the steps:
(1) get and carried bilirubinic Fel Sus domestica tankage, through saponification, hydrolysis, decolouring and after being dried, obtain tan pig TOTAL BILE ACID crude product;
(2) get pig TOTAL BILE ACID crude product, add esterifying reagent, under catalyst action, carry out esterification and generate pig TOTAL BILE ACID ester;
(3) under alkaline condition with ethanol-extracted pig TOTAL BILE ACID ester;
(4) pig TOTAL BILE ACID ester is carried out to recrystallization, the white powder that obtains pig TOTAL BILE ACID ester is dried to constant weight under infrared lamp;
(5) get the pig TOTAL BILE ACID ester that above-mentioned (4) make, to the reaction that is hydrolyzed under alkaline condition of pig TOTAL BILE ACID ester, the white crystal that recrystallization is obtained is dried to constant weight under infrared lamp, can make Hyodeoxycholic Acid.
As improvement of the present invention, the esterifying reagent of above-mentioned steps (2) is a kind of of methyl alcohol, ethanol and Virahol.
As the further improvement of the present invention, the esterifying reagent of above-mentioned steps (2) is anhydrous methanol, and its consumption is 5～10ml/g.
As improvement of the present invention, the catalyzer of above-mentioned steps (2) is 98% vitriol oil, and the mol ratio of itself and raw material is 0.1:1.
As improvement of the present invention, the alkali of above-mentioned steps (3) is NaOH, and the mol ratio of itself and pig TOTAL BILE ACID ester is 2.5:1.
As improvement of the present invention, the recrystallization reagent that above-mentioned steps (4) is used is benzene or toluene.
As improvement of the present invention, the recrystallization reagent that above-mentioned steps (5) is used is ethyl acetate.
Compared with prior art, beneficial effect of the present invention is:
The present invention is usingd Fel Sus domestica as extracting raw material, and Fel Sus domestica raw material is extensively easy to get, and has reduced preparation cost.In extraction process of the present invention, choosing methyl alcohol is solvent and esterifying reagent, determine the hydrolysis of Hyodeoxycholic Acid methyl esters and refining condition, determine and adopt sodium hydroxide as alkaline catalysts, raw material and its feed ratio are 1:2.5, through this technical process, the total recovery of Hyodeoxycholic Acid reaches more than 40%.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only, for helping to understand the present invention, should not be considered as concrete restriction of the present invention.
In the following example, the same meaning that all specialties of using and scientific words and those skilled in the art are familiar.
A method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage, comprises the steps:
(1) get and carried bilirubinic Fel Sus domestica tankage, through saponification, hydrolysis, decolouring and after being dried, obtain tan pig TOTAL BILE ACID crude product;
(2) get pig TOTAL BILE ACID crude product, add esterifying reagent, under catalyst action, carry out esterification and generate pig TOTAL BILE ACID ester;
(3) under alkaline condition with ethanol-extracted pig TOTAL BILE ACID ester;
(4) pig TOTAL BILE ACID ester is carried out to recrystallization, the white powder that obtains pig TOTAL BILE ACID ester is dried to constant weight under infrared lamp;
(5) get the pig TOTAL BILE ACID ester that above-mentioned (4) make, to the reaction that is hydrolyzed under alkaline condition of pig TOTAL BILE ACID ester, the white crystal that recrystallization is obtained is dried to constant weight under infrared lamp, can make Hyodeoxycholic Acid.
Embodiment 1
Get 250ml round-bottomed flask, add pig TOTAL BILE ACID crude product 10g, anhydrous methanol 50ml, 98% vitriol oil 0.7ml, stirring reaction 24h under normal temperature, complete through TLC detection reaction, without the residual rear stopped reaction of raw material, in system, add anhydrous Na HCO
3solid adjusts pH to neutral, elimination inorganic salt, filter cake methanol wash, merging filtrate and washing lotion, reclaim under reduced pressure methyl alcohol, obtain brown dope, add water 50ml to dissolve wherein remaining inorganic salt, then extract organism (50ml with ether gradation, 30ml, 20ml), merge organic phase, respectively with saturated NaHCO
3solution and saturated common salt water washing 1 time, anhydrous Na
2sO
4dry 2h, filters, and removes ether under reduced pressure, obtain brown thick thing 11.4g, in flask, add benzene 30ml, at 80 ℃ of oil bath pans, after dissolve complete, stop heating, after naturally cooling to room temperature, put into the about 16h of refrigerator, separate out solid, filter, filter cake is with benzene washing 3 times, obtain off-white color solid 4.9g, then carry out recrystallization with benzene, the white powder obtaining is dried to constant weight under infrared lamp, for 4.5g, i.e. pig TOTAL BILE ACID methyl esters;
Get 100ml round-bottomed flask, add successively Hyodeoxycholic Acid methyl esters (4.5g), NaOH solid (1.1g), ethanol 30ml, water 1ml, stirring and refluxing reaction 20h at 80 ℃, after completion of the reaction, decompression and solvent recovery, to dry, obtains faint yellow solid in TLC monitoring, add water 30ml, under vigorous stirring, add 10% dilute hydrochloric acid and adjust pH to 1.5, separate out a large amount of solids, continue to stir at normal temperatures 0.5h, filter, 10% dilute hydrochloric acid washing 3 times for filter cake, washes 3 times, obtains block white solid, drying under reduced pressure 8h at 50 ℃ is 4.5g.With re-crystallizing in ethyl acetate, after the white crystal obtaining is dried to constant weight under infrared lamp, for 4g, mp is 200～201 ℃, i.e. Hyodeoxycholic Acid, total recovery 45%.
Embodiment 2
Get 250ml round-bottomed flask, add pig TOTAL BILE ACID crude product 10g, anhydrous methanol 100ml, 98% vitriol oil 0.7ml, stirring reaction 36h under normal temperature, complete through TLC detection reaction, without the residual rear stopped reaction of raw material, in system, add anhydrous Na HCO
3solid adjusts pH to neutral, elimination inorganic salt, filter cake methanol wash, merging filtrate and washing lotion, reclaim under reduced pressure methyl alcohol, obtain brown dope, add water 50ml to dissolve wherein remaining inorganic salt, then extract organism (50ml with ether gradation, 30ml, 20ml), merge organic phase, respectively with saturated NaHCO
3solution and saturated common salt water washing 1 time, anhydrous Na
2sO
4dry 2h, filters, and removes ether under reduced pressure, obtain brown thick thing 11g, in flask, add benzene 30ml, at 80 ℃ of oil bath pans, after dissolve complete, stop heating, after naturally cooling to room temperature, put into the about 16h of refrigerator, separate out solid, filter, filter cake is with benzene washing 3 times, obtain off-white color solid 4.7g, then carry out recrystallization with benzene, the white powder obtaining is dried to constant weight under infrared lamp, for 4.4g, i.e. pig TOTAL BILE ACID methyl esters;
Get 100ml round-bottomed flask, add successively Hyodeoxycholic Acid methyl esters (4.4g), NaOH solid (1.1g), ethanol 30ml, water 1ml, stirring and refluxing reaction 20h at 80 ℃, after completion of the reaction, decompression and solvent recovery, to dry, obtains faint yellow solid in TLC monitoring, add water 30ml, under vigorous stirring, add 10% dilute hydrochloric acid and adjust pH to 1.5, separate out a large amount of solids, continue to stir at normal temperatures 0.5h, filter, 10% dilute hydrochloric acid washing 3 times for filter cake, washes 3 times, obtains block white solid, drying under reduced pressure 8h at 50 ℃ is 4.0g.With re-crystallizing in ethyl acetate, after the white crystal obtaining is dried to constant weight under infrared lamp, for 4g, mp is 200～201 ℃, i.e. Hyodeoxycholic Acid, total recovery 40%.
Embodiment 3
Get 250ml round-bottomed flask, add pig TOTAL BILE ACID crude product 10g, anhydrous methanol 80ml, 98% vitriol oil 0.7ml, stirring reaction 36h under normal temperature, complete through TLC detection reaction, without the residual rear stopped reaction of raw material, in system, add anhydrous Na HCO
3solid adjusts pH to neutral, elimination inorganic salt, filter cake methanol wash, merging filtrate and washing lotion, reclaim under reduced pressure methyl alcohol, obtain brown dope, add water 50ml to dissolve wherein remaining inorganic salt, then extract organism (50ml with ether gradation, 30ml, 20ml), merge organic phase, respectively with saturated NaHCO
3solution and saturated common salt water washing 1 time, anhydrous Na
2sO
4dry 2h, filters, and removes ether under reduced pressure, obtain brown thick thing 11.2g, in flask, add benzene 30ml, at 80 ℃ of oil bath pans, after dissolve complete, stop heating, after naturally cooling to room temperature, put into the about 16h of refrigerator, separate out solid, filter, filter cake is with toluene wash 3 times, obtain off-white color solid 4.6g, then carry out recrystallization with toluene, the white powder obtaining is dried to constant weight under infrared lamp, for 4.4g, i.e. pig TOTAL BILE ACID methyl esters;
Get 100ml round-bottomed flask, add successively Hyodeoxycholic Acid methyl esters (4.4g), NaOH solid (1.1g), ethanol 30ml, water 1ml, stirring and refluxing reaction 20h at 80 ℃, after completion of the reaction, decompression and solvent recovery, to dry, obtains faint yellow solid in TLC monitoring, add water 30ml, under vigorous stirring, add 10% dilute hydrochloric acid and adjust pH to 1～2, separate out a large amount of solids, continue to stir at normal temperatures 0.5h, filter, 10% dilute hydrochloric acid washing 3 times for filter cake, washes 3 times, obtains block white solid, drying under reduced pressure 6～8h at 50 ℃ is 4.2g.With re-crystallizing in ethyl acetate, after the white crystal obtaining is dried to constant weight under infrared lamp, for 4.2g, mp is 200～201 ℃, i.e. Hyodeoxycholic Acid, total recovery 42%.
Embodiment 4
Get 250ml round-bottomed flask, add pig TOTAL BILE ACID crude product 10g, anhydrous methanol 100ml, 98% vitriol oil 0.7ml, stirring reaction 36h under normal temperature, complete through TLC detection reaction, without the residual rear stopped reaction of raw material, in system, add anhydrous Na HCO
3solid adjusts pH to neutral, elimination inorganic salt, filter cake methanol wash, merging filtrate and washing lotion, reclaim under reduced pressure methyl alcohol, obtain brown dope, add water 50ml to dissolve wherein remaining inorganic salt, then extract organism (50ml with ether gradation, 30ml, 20ml), merge organic phase, respectively with saturated NaHCO
3solution and saturated common salt water washing 1 time, anhydrous Na
2sO
4dry 2h, filters, and removes ether under reduced pressure, obtain brown thick thing 11.2g, in flask, add benzene 30ml, at 80 ℃ of oil bath pans, after dissolve complete, stop heating, after naturally cooling to room temperature, put into the about 16h of refrigerator, separate out solid, filter, filter cake is with toluene wash 3 times, obtain off-white color solid 4.4g, then carry out recrystallization with toluene, the white powder obtaining is dried to constant weight under infrared lamp, for 4.3g, i.e. pig TOTAL BILE ACID methyl esters;
Get 100ml round-bottomed flask, add successively Hyodeoxycholic Acid methyl esters (4.3g), NaOH solid (1.1g), ethanol 30ml, water 1ml, stirring and refluxing reaction 20h at 80 ℃, after completion of the reaction, decompression and solvent recovery, to dry, obtains faint yellow solid in TLC monitoring, add water 30ml, under vigorous stirring, add 10% dilute hydrochloric acid and adjust pH to 1.5, separate out a large amount of solids, continue to stir at normal temperatures 0.5h, filter, 10% dilute hydrochloric acid washing 3 times for filter cake, washes 3 times, obtains block white solid, drying under reduced pressure 8h at 50 ℃ is 4.2g.With re-crystallizing in ethyl acetate, after the white crystal obtaining is dried to constant weight under infrared lamp, for 4g, mp is 200～201 ℃, i.e. Hyodeoxycholic Acid, total recovery 40%.
Applicant's statement, person of ordinary skill in the field is on the basis of above-described embodiment, by the concrete content point value of above-described embodiment component, combined with the technical scheme of summary of the invention part, thereby the new numerical range producing, also be one of record scope of the present invention, the application, for making specification sheets simple and clear, is no longer enumerated these numerical ranges.
Claims (7)
1. from remove bilirubinic Fel Sus domestica tankage, extract a method for Hyodeoxycholic Acid, it is characterized in that, comprise the steps:
(1) get and carried bilirubinic Fel Sus domestica tankage, through saponification, hydrolysis, decolouring and after being dried, obtain tan pig TOTAL BILE ACID crude product;
(2) get pig TOTAL BILE ACID crude product, add esterifying reagent, under catalyst action, carry out esterification and generate pig TOTAL BILE ACID ester;
(3) under alkaline condition with ethanol-extracted pig TOTAL BILE ACID ester;
(4) pig TOTAL BILE ACID ester is carried out to recrystallization, obtain the white powder of pig TOTAL BILE ACID ester, under infrared lamp, be dried to constant weight;
(5) get the pig TOTAL BILE ACID ester that above-mentioned (4) make, to the reaction that is hydrolyzed under alkaline condition of pig TOTAL BILE ACID ester, the white crystal that recrystallization is obtained is dried to constant weight under infrared lamp, can make Hyodeoxycholic Acid.
2. a kind of method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage as claimed in claim 1, is characterized in that: the esterifying reagent of described step (2) is a kind of of methyl alcohol, ethanol and Virahol.
3. a kind of method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage as claimed in claim 1, is characterized in that: the esterifying reagent of described step (2) is anhydrous methanol, and its consumption is 5～10ml/g.
4. a kind of method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage as claimed in claim 1, is characterized in that: the catalyzer of described step (2) is 98% vitriol oil, and the mol ratio of itself and raw material is 0.1:1.
5. a kind of method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage as claimed in claim 1, is characterized in that: the alkali of described step (3) is NaOH, and the mol ratio of itself and pig TOTAL BILE ACID ester is 2.5:1.
6. a kind of method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage as claimed in claim 1, is characterized in that: the recrystallization reagent that described step (4) is used is benzene or toluene.
7. a kind of method of extracting Hyodeoxycholic Acid from remove bilirubinic Fel Sus domestica tankage as claimed in claim 1, is characterized in that: the recrystallization reagent that described step (5) is used is ethyl acetate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108459104A (en) * | 2017-12-26 | 2018-08-28 | 华南师范大学 | A kind of method of personal care articles in detection Fish Bile |
| CN110179044A (en) * | 2019-05-23 | 2019-08-30 | 江南大学（如皋）食品生物技术研究所 | A kind of method that hardship intestines alkaline process takes off hardship |
| CN111961105A (en) * | 2020-09-23 | 2020-11-20 | 安徽科宝生物工程有限公司 | Method for separating hyodeoxycholic acid from pig bile paste by extraction method |
-
2013
- 2013-09-27 CN CN201310449477.3A patent/CN103539828A/en active Pending
Non-Patent Citations (2)
| Title |
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| 赵松华等: "《猪去氧胆酸精品的生产工艺》", 《中国药业》 * |
| 邓启华等: "《猪胆汁中三种主要胆汁酸的提取分离》", 《中国生化药物杂志》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108459104A (en) * | 2017-12-26 | 2018-08-28 | 华南师范大学 | A kind of method of personal care articles in detection Fish Bile |
| CN110179044A (en) * | 2019-05-23 | 2019-08-30 | 江南大学（如皋）食品生物技术研究所 | A kind of method that hardship intestines alkaline process takes off hardship |
| CN111961105A (en) * | 2020-09-23 | 2020-11-20 | 安徽科宝生物工程有限公司 | Method for separating hyodeoxycholic acid from pig bile paste by extraction method |
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Application publication date: 20140129 |